JP3273657B2 - Vinylcyclopropanone cyclic acetal compound and its polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel vinylcyclopropanone cyclic acetal compound and a poly (vinylcyclopropane acetal). The compound of the present invention is a novel compound and is useful as a raw material for molding materials, composite materials, casting materials, sealing materials, medical materials, dental materials, paints and adhesives.

[0002]

2. Description of the Related Art It is well known that polymerizable monomers such as acrylonitrile, vinyl acetate, methyl methacrylate, styrene, ethylene oxide and epichlorohydrin are accompanied by a large volume shrinkage. Further, volume shrinkage when a thermosetting resin such as an epoxy resin or a phenol resin is cured has become a major problem in the fields of casting materials, sealing materials, adhesive materials, and the like.

[0003] If a material which is non-shrinkable or shows extremely small shrinkage upon curing can be obtained, dimensional accuracy can be improved, precision molding can be performed by reducing warpage, distortion, and gap generation, and material strength and adhesion can be improved by reducing internal stress. Etc. can be expected.

[0004] With respect to several kinds of bicyclo orthoesters, spiro orthoesters and spiroorthocarbonate compounds, it has been reported that the volume reduction during ring-opening polymerization is extremely small or the volume expands. Attention has been paid to application to the use [Takeshi Endo, Toshikazu Takada, Journal of the Petroleum Institute, Vol. 32, p. 237 (1989)].

[0005] Efficient ring-opening polymerization of bicycloorthoesters, spiroorthoesters, and spiroorthocarbonate compounds includes a Lewis acid such as boron trifluoride / ether complex and / or a benzene such as trifluoromethanesulfonic acid. A method by cationic polymerization using a Sted acid as a polymerization initiator is known.

[0006]

The cation ring-opening polymerization of bicyclo orthoesters, spiro orthoesters, and spiro orthocarbonate compounds using Lewis acids and / or Bronsted acids as polymerization initiators involves Lewis acids and Bronsted acids. Is usually a strong acid, so it is difficult to handle, and the effect of moisture on the polymerization is large, and there are problems such as coloring of the obtained polymer, corrosiveness and toxicity of acid components remaining in the polymer. On the other hand, the above-mentioned problem is not found in radical polymerization using an organic polymerization initiator such as an azo polymerization initiator or a peroxide polymerization initiator. However, ordinary bicyclo orthoesters, spiro orthoesters, Radical ring-opening polymerization of the orthocarbonate compound does not proceed. As one of the monomers having radical ring-opening polymerizability, a vinylcyclopropane compound has been reported. However, its polymerization shrinkage is relatively large. [Fumio Mita, Toshikazu Takada, Tsuyoshi Endo, 63rd Annual Meeting of the Chemical Society of Japan 1A
1 12 (1992)]).

An object of the present invention is to provide a vinylcyclopropanone cyclic acetal compound and a poly (vinylcyclopropane acetal) which undergo ring-opening polymerization or cross-linking by radical polymerization and have a small volume shrinkage at that time. .

[0008]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have conducted intensive studies on compounds which undergo ring-opening polymerization or cross-linking by radical polymerization and have a small volume shrinkage at that time. The present inventors have found that a vinylcyclopropanone cyclic acetal compound and poly (vinylcyclopropane acetal) satisfy the above conditions, and have completed the present invention.

That is, the present invention provides the following general formulas (1) to (1)
It relates to a vinylcyclopropanone cyclic acetal compound represented by 4).

[0010]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0012]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0014]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0016]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0018]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0020]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0022]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0024]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0026]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0028]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0030]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0032]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0034]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0036]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

Further, the present invention provides a compound represented by the following general formula (15):
It relates to poly (vinylcyclopropane acetal) represented by (28).

[0039]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0041]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0043]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0045]

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(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0047]

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(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0049]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0051]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0053]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0055]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0057]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0059]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0061]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.

[0063]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

[0065]

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(Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)

In the general formulas (1) to (28), R ¹ ,
As the lower alkyl group represented by R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , an alkyl group having 8 or less carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n- Butyl group, i-butyl group, t-butyl group, n-
Examples include a pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group.

Preferred examples of the vinylcyclopropanone cyclic acetal compound of the present invention include the following compounds.

[0069]

Embedded image Preferred examples of the poly (vinylcyclopropane acetal) of the present invention include the following compounds.

[0070]

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It should be noted that the vinylcyclopropanone cyclic acetal compound and poly (vinylcyclopropane acetal) of the present invention may be used not only as a single compound but also as a mixture of two or more compounds.

[0072] The vinylcyclopropanone cyclic acetal compound and poly (vinylcyclopropane acetal) of the present invention may be used as a mixture with other polymerizable monomers. The other polymerizable monomer may be any having radical polymerizability, and preferred examples thereof include (meth) acrylic acid; methyl (meth) acrylate, n- or i-propyl (meth) acrylate, and (meth) acrylic acid. Acrylic acid n-
Or (meth) acrylates such as i- or t-butyl, 2-hydroxyethyl methacrylate (HEMA); ethylene glycol, propanediol, butanediol, hexanediol, octanediol,
Di (meth) acrylates of diols such as decanediol, eicosanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dodecaethylene glycol, tetradecaethylene glycol;
2,2-bis [4- (3-methacryloyloxy-2-hydroxypropoxy) phenyl] propane (Bis-GM
A), bisphenol A dimethacrylate, 2,2-di (4-methacryloxypolyethoxyphenyl) propane (ethoxy groups 2 to 10 in one molecule), 1,2-bis (3-
Di (meth) acrylates such as methacryloxy-2-hydroxypropoxy) butane; (meth) acrylonitrile;
(Meth) acrylamide; vinyl chloride; vinyl acetate; styrene and the like.

The methods for producing the vinylcyclopropanone cyclic acetal compounds represented by the general formulas (1) to (14) and the poly (vinylcyclopropane acetal) represented by the general formulas (15) to (28) are described below. It is on the street.

That is, a dihalovinylcyclopropane compound represented by the following general formula (29) and the following chemical formula (3)
It is produced by a dehydrohalogenation reaction using a base with a diol represented by (0) to (43).

[0075]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom, a lower alkyl group or a halogen group, and X represents a halogen group.

[0077]

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[0078]

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[0079]

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[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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In this reaction, a vinylcyclopropanone cyclic acetal compound and poly (vinylcyclopropane acetal) are simultaneously formed. It is unexpected that low-molecular compounds and high-molecular compounds are produced simultaneously by such a reaction mechanism, and is a novel finding of the present inventors.

The method for isolating the vinylcyclopropanone cyclic acetal compound and the poly (vinylcyclopropane acetal) is not particularly limited. For example, the vinylcyclopropanone cyclic acetal compound can be isolated from the reaction mixture by distillation. (Vinylcyclopropane acetal) can be isolated by reprecipitation or preparative gel permeation chromatography.

In the dehydrohalogenation reaction of a dihalovinylcyclopropane compound represented by the general formula (29) with a diol represented by the chemical formulas (30) to (43) using a base, both compounds are treated with lithium hydride. , Sodium hydride, potassium hydride and the like. It is preferred that the dihalovinylcyclopropane compound and the diol compound are mixed in equimolar amounts. The base is 200 to 600 mol%, preferably 2 mol%, based on the diol compound.
It is used in the range of 00 to 300 mol%.

The reaction temperature is in the range of -78 to 100 ° C, preferably -20 to 50 ° C. The reaction is usually performed in an atmosphere of an inert gas such as nitrogen, argon, and helium.

The above reaction may be carried out in the absence of a solvent, but the reaction is carried out in the presence of an aprotic solvent such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, etc. It is preferable in terms of easiness and the like. It should be noted that by increasing the amount of the solvent used, it is possible to increase the production ratio of the vinylcyclopropanone cyclic acetal compound to poly (vinylcyclopropane acetal). Conversely, by reducing the amount of the solvent used, the production ratio of poly (vinylcyclopropane acetal) to the vinylcyclopropanone cyclic acetal compound can be increased.

The reaction time is usually selected from the range of 1 to 100 hours. After reaching the desired conversion, the reaction solution is washed with water, and then the vinylcyclopropanone cyclic acetal compound and poly (vinylcyclopropane acetal) obtained by a known method are isolated and purified.

The cyclic acetal compound of vinylcyclopropanone and poly (vinylcyclopropane acetal) of the present invention include azobisisobutyronitrile, methyl azobisisobutyrate, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile and the like. Azo polymerization initiators of the following: diisopropyl peroxydicarbonate, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, benzoyl peroxide, cyclohexanone peroxide, t-butyl perbenzoate,
Dicumyl peroxide, di-t-butyl peroxide,
Ring-opening polymerization or cross-linking is performed by a radical polymerization initiator such as a peroxide-based polymerization initiator such as p-menthane hydroperoxide, pinane hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide.

Also, benzophenone, Michler's ketone,
Aromatic ketones such as xanthone, thioxanthone, 2-chlorothioxanthone and 2-ethylanthraquinone; acetophenone, trichloroacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2
-Methyl-4'-isopropylpropiophenone, 1-
Ultraviolet radical polymerization using an initiator such as acetophenones such as hydroxycyclohexyl phenyl ketone, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-diethoxyacetophenone, and 2,2-dimethoxy-2-phenyl-acetophenone benzyl dimethyl ketal; , Norcan furquinone / N, N-
Visible light radical polymerization using an α-diketone / amine initiator such as dimethylaminoethyl methacrylate, camphorquinone / N, N-dimethylaminoethyl methacrylate, camphorquinone / ethyl p-N, N-dimethylaminobenzoate is also used. Is done.

The radical polymerization initiator is used in an amount of 0.01 to 10 based on the vinylcyclopropanone cyclic acetal compound or poly (vinylcyclopropane acetal).
Mol%, preferably in the range of 0.05 to 3 mol%.

The temperature of the radical polymerization or the crosslinking reaction varies depending on the type of the radical polymerization initiator used.
Temperatures in the range from room temperature to 200 ° C, preferably 50 to 180 ° C, are selected.

The radical polymerization or crosslinking reaction can be carried out under any pressure from reduced pressure to increased pressure, but is preferably carried out at normal pressure.

The radical polymerization or cross-linking reaction may be carried out in the absence of a solvent. However, aromatic hydrocarbons such as benzene, toluene, xylene, hemimelitene, pseudocumene and mesitylene; and aliphatic hydrocarbons such as hexane, heptane and octane. Hydrogen; an alicyclic hydrocarbon such as cyclohexane and cyclooctane; and a solvent such as a halogenated hydrocarbon such as methylene chloride, chloroform, tetrachloroethylene, chlorobenzene, dichlorobenzene, and trichlorobenzene may be used.

The radical polymerization or crosslinking reaction time is usually selected from the range of 1 to 100 hours. After reaching the desired degree of polymerization or cross-linking, the polymer obtained is isolated and purified by known methods.

[0104]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In addition, the physical property value was measured by the following method. ¹ H-NMR: JNM-EX-90 manufactured by JEOL (measurement frequency: 9
0 MHz) ¹³ C-NMR: JNM-EX-90 manufactured by JEOL (measurement frequency; 22.5 MHz) IR: Fourier transform infrared spectrophotometer FT manufactured by JASCO
/ IR-3 type Elemental analysis: CHN-coder MT2 type manufactured by Yanagimoto Seisakusho Weight average molecular weight: GPC-8000 system manufactured by Tosoh (polystyrene gel column; TSK gel G5000HX)
L, G4000HXL, G2500HXL, mobile phase solvent; THF, flow rate: 1.0 mL / min, detector: RI, polystyrene equivalent) Density: Density gradient tube method specific gravity measuring apparatus A type (density gradient liquid; manufactured by Shibayama Scientific Instruments) (Aqueous calcium bromide solution, measurement temperature: 25 ° C)

Example 1 To a dispersion of sodium hydride (4.32 g, 180 mmol) in DMF (150 mL) was added D. of ethylene glycol (4.66 g, 75.0 mmol).
After adding the MF (40 mL) solution at room temperature over 30 minutes, 1,1-dichloro-2-vinylcyclopropane (10.3 g, 75.0 mmol) was added.
DMF (80 mL) solution was added over 30 minutes at room temperature. 1 at room temperature
After stirring for 2 hours, water (800 mL) was added, and ether (400 mL) was added.
mL). The organic phase was washed twice with a saturated aqueous sodium hydrogen carbonate solution (800 mL), dried over anhydrous sodium sulfate, concentrated, and distilled under reduced pressure to obtain 1-vinyl-4,7-dioxaspiro [2.4] heptane; Rate 4.14 g (44%), bp 100-1
02 ° C / 135 mmHg, ¹ H NMR (CDCl ₃ ): 1.03 (dd, J = 6.8 H
z, 6.8 Hz, 1 H), 1.37 (dd, J = 6.8 Hz, 10.0 Hz, 1
H), 1.68-1.97 (m, 1 H), 3.87-4.12 (m, 4 H), 4.90-
5.77 (m, 3 H) ppm, ¹³ C NMR (CDCl ₃ ): 15.19, 25.9
9, 64.81, 65.15, 96.72, 114.10, 135.47 ppm, IR (ne
at) 3083, 2979, 2894, 1637, 1456, 1363, 1267, 119
5, 1166, 1064, 1012, 700 cm ^-1 . Calculated value for elemental analysis C
_{. 7 H 10 O 2: C} , 66.65: H, 7.99 Found: C, 66.77;
H, 8.07.

Example 2 Synthesis of 1,4-butanediol (3.17 g, 35.2 mmol) and 1,1-dichloro-2-vinylcyclopropane (4.82 g, 35.2 mmol) in the same manner as in Example 1 -Vinyl-4,9-dioxaspiro [2.6] nonane was obtained; yield 700 mg (13%), bp 8
9 ° C./55 mmHg, ¹ H NMR (CDCl ₃ ): 0.90 (dd, J = 6.6 H
z, 5.5 Hz, 1 H), 1.23 (dd, J = 5.5 Hz, 10.0 Hz, 1
H), 1.66-2.02 (m, 5 H), 3.76-3.87 (m, 4 H), 4.91-
5.78 (m, 3 H) ppm, ¹³ C NMR (CDCl ₃ ): 20.24, 28.9
6, 29.07, 29.22, 66.59, 67.15, 92.60, 114.12, 136.
23 ppm, IR (neat) 3081, 3004, 2944, 2879, 2844, 16
37, 1440, 1338, 1267, 1168, 1085, 1012, 983 c
m ^-1 Analysis Calculated _{C 9 H 14 O 2:.} C, 70.10: H, 9.
15. Found: C, 69.83; H, 9.31.

Example 3 1-phenyl-1,2-ethanediol (10.4 g, 75.0 mmol) and 1,1-dichloro-2-vinylcyclopropane (10.3 g, 7
5.0 mmol) and synthesized in the same manner as in Example 1.
5-phenyl-4,7-dioxaspiro [2.4] heptane was obtained;
Yield 10.3 g (68%), bp 93-94 ° C / 0.3 mmHg, ¹ H NMR (C
DCl ₃ ): 0.99-1.27 (m, 1 H), 1.32-1.63 (m, 1 H), 1.
76-2.07 (m, 1 H), 3.67-3.95 (m, 1 H), 4.20-4.48
(m, 1 H), 4.93-5.26 (m, 3 H), 5.44-5.83 (m, 1 H),
7.35 (s, 5 H) ppm, IR (neat) 3083, 3063, 3032, 300
5, 2981, 2886, 1636, 1453, 1360, 1263, 1016, 757,
699 cm ^-1 . Calculated value for elemental analysis: C ₁₃ H ₁₄ O ₂ : C, 77.2
0: H, 6.98. Found: C, 76.78; H, 7.04.

Example 4 1,2-benzenedimethanol (10.4 g, 75.0 mmol) and
1,1-dichloro-2-vinylcyclopropane (10.3 g, 75.0 m
mol) from 1-vinyl-6,7-
Benzo-4,9-dioxaspiro [2.6] nonane was obtained; yield 5.
83g (38%), bp98 ℃ / 0.3 mmHg, mp 61-62 ℃, 1 H NMR
(CDCl ₃ ): 1.30-1.44 (m, 1 H), 1.61-1.79 (m, 1 H),
2.20-2.53 (m, 1 H), 5.20 (s, 4 H), 5.21-5.60 (m,
2 H), 5.76-6.16 (m, 1 H) 7.48 (s, 4 H) ppm, IR (KB
r) 2928, 2866, 1636, 1338, 1169, 1167, 1042, 1028,
776, 742, 620 cm ^-1. Analysis Calculated C ₁₃ H ₁₄ O
₂ : C, 77.20: H, 6.98. Found: C, 77.20; H, 6.98.

Reference Example 1 252 mg of 1-vinyl-4,7-dioxaspiro [2.4] heptane obtained in Example 1, 8.8 mg of di-t-butyl peroxide and 2 mL of chlorobenzene were charged into a glass vessel, and degassed. After sealing, the mixture was heated at 120 ° C. for 48 hours to obtain a pale yellow transparent liquid. This liquid was dissolved in 2 mL of methylene chloride, and the polymer was isolated using a preparative liquid chromatograph. The weight average molecular weight of the obtained polymer was 5,900. Product I
When the R spectrum was measured, absorption at 1733 cm ^-1 due to the ester group of the ring-opened polymer having the structure of the following structural formula (44) was observed. The volume shrinkage calculated from the density of the monomer and the polymer was 7.0%.

[0110]

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Reference Example 2 308 mg of 1-vinyl-4,9-dioxaspiro [2.6] nonane, 8.8 mg of di-t-butyl peroxide and 2 mL of chlorobenzene obtained in Example 2 were charged into a glass vessel, and degassed. After sealing, the mixture was heated at 120 ° C. for 48 hours to obtain a pale yellow transparent liquid. This liquid was dissolved in 2 mL of methylene chloride, and the polymer was isolated using a preparative liquid chromatograph. The weight average molecular weight of the obtained polymer was 6,200. Product I
When the R spectrum was measured, absorption at 1733 cm ^-1 due to the ester group of the ring-opened polymer having the structure of the following structural formula (45) was observed. The volume shrinkage during polymerization calculated from the density of the monomer and the polymer was 6.8%.

[0112]

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Reference Example 3 1-vinyl-5-phenyl-4,7-dioxaspiro [2.4] heptane 404 mg obtained in Example 3, di-t-butyl peroxide
8.8 mg and 2 mL of chlorobenzene were charged into a glass container, degassed, sealed, and heated at 120 ° C for 48 hours to obtain a pale yellow transparent liquid. This liquid was dissolved in 2 mL of methylene chloride, and the polymer was isolated using a preparative liquid chromatograph. The weight average molecular weight of the obtained polymer was 7,400. The IR spectrum of the product was measured to be 1733.
At cm ⁻¹ , absorption due to an ester group of the ring-opening polymer having the structure of the following structural formula (46) was observed. The volumetric shrinkage during polymerization calculated from the monomer and polymer densities is 6.
It was 0%.

[0114]

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Reference Example 4 404 mg of 1-vinyl-5-phenyl-4,7-dioxaspiro [2.4] heptane and 8.8 mg of di-t-butyl peroxide obtained in Example 3 were charged into a glass vessel, and degassed. After sealing, 12
Heating at 0 ° C. for 48 hours gave a pale yellow transparent liquid. This liquid was dissolved in 2 mL of methylene chloride, and the polymer was isolated using a preparative liquid chromatograph. The weight average molecular weight of the obtained polymer was 7,300. When the IR spectrum of the product was measured, absorption due to the ester group of the ring-opening polymer having the structure of the above structural formula (46) was observed at 1733 cm ⁻¹ . The volume shrinkage during polymerization calculated from the density of the monomer and the polymer was 6.5%.

Reference Example 5 1-vinyl-6,7-benzo-4,9-dioxaspiro [2.6] nonane 404 mg and di-t-butyl peroxide 8.8 mg obtained in Example 4 were charged into a glass container, Qi, after sealed tube, 120
Heating at 48 ° C for 48 hours gave a pale yellow transparent liquid. This liquid was dissolved in 2 mL of methylene chloride, and the polymer was isolated using a preparative liquid chromatograph. The weight average molecular weight of the obtained polymer was 9,200. When the IR spectrum of the product was measured, absorption at 1733 cm ^-1 due to the ester group of the ring-opened polymer having the structure of the following structural formula (47) was observed. The volume shrinkage during polymerization calculated from the densities of the monomer and the polymer was 2.9%.

[0117]

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Reference Example 6 404 mg of 1-vinyl-6,7-benzo-4,9-dioxaspiro [2.6] nonane and 8.8 mg of di-t-butyl peroxide obtained in Example 4 were charged into a glass container, Qi, after sealed tube, 120
Heating at 48 ° C for 48 hours gave a pale yellow transparent liquid. This liquid was dissolved in 2 mL of methylene chloride, and the polymer was isolated using a preparative liquid chromatograph. The weight average molecular weight of the obtained polymer was 10,100. When the IR spectrum of the product was measured, absorption due to the ester group of the ring-opened polymer having the structure of the above structural formula (47) was observed at 1733 cm ⁻¹ . The volume shrinkage during polymerization calculated from the density of the monomer and the polymer was 3.2%.

Example 5 To a dispersion of sodium hydride (1.73 g, 72.0 mmol) in DMF (30 mL) was added 1,4-butanediol (2.70 g, 30.0 mmol) in DMF.
After adding the MF (30 mL) solution at 0 ° C. over 30 minutes, 1,1-dichloro-2-vinylcyclopropane (4.11 g, 30.0 mmol) was added.
DMF (30 mL) solution was added at 0 ° C. over 30 minutes. 1 at room temperature
After stirring for 2 hours, water (180 mL) was added, and ether (90 mL) was added.
mL). The organic phase was washed twice with a saturated aqueous sodium hydrogen carbonate solution (180 mL), dried over anhydrous sodium sulfate, concentrated, distilled under reduced pressure, and the polymer was isolated by preparative HPLC (solvent; THF); 1.34 g (29%), weight average molecular weight 5080, ¹ H NMR (CDCl3): 0.78-0.91 (m, 1 H), 1.11-
1.28 (m, 1 H), 1.40-2.00 (m, 5 H), 3.30-3.90 (m, 4
H), 4.87-5.75 (m, 3 H) ppm,, IR (neat) 3081, 300
6, 2942, 2873, 1860, 1637, 1446, 1338, 1263, 1182,
1043, 900 cm ^-1 .Calculated value for elemental analysis C9H14O2: C, 70.1
0: H, 9.15. Found: C, 70.02; H, 9.23.

Example 6 Methanonaphthalene-2,3-dimethanol (16.7 g, 75.0 mmol
l) and 1,1-dichloro-2-vinylcyclopropane (10.3
g, 75.0 mmol), except that the polymer was isolated by dissolving it in methylene chloride and reprecipitating it in a mixed solution of methanol / triethylamine (volume ratio; 100/1). Yield: 11.0 g (51%), weight average molecular weight: 8090, ¹ H NMR (CDCl3): 0.70-2.50 (m, 19
H), 3.00-3.80 (m, 4 H), 4.80-5.80 (m, 3 H) ppm, IR
(KBr) 3079, 3047, 2942, 2883, 1859, 1637, 1469, 1
448, 1332, 1267, 1184, 1041, 896 cm ^-1 . Calculated for elemental analysis: C19H26O2: C, 79.68: H, 9.15. Found: C, 79.7
7; H, 9.10.

Reference Example 7 A glass container was charged with 308 mg of the polymer obtained in Example 5 and 8.8 mg of di-t-butyl peroxide.
Heating at 0 ° C. for 48 hours gave a pale yellow transparent solid. This solid was subjected to Soxhlet extraction with methylene chloride. The volume shrinkage calculated from the polymer density before and after the reaction was 3.5%.

Reference Example 8 A glass container was charged with 308 mg of the polymer obtained in Example 5 and 10 mg of azobisisobutyronitrile.
Heating at 48 ° C. for 48 hours gave a pale yellow transparent solid. This solid was subjected to Soxhlet extraction with methylene chloride. The volume shrinkage calculated from the polymer density before and after the reaction was 1.9%.

Reference Example 9 572 mg of the polymer obtained in Example 6, 15 m of benzoyl peroxide
g, 1 mL of chlorobenzene into a glass container, degas,
After sealing, the mixture was heated at 80 ° C. for 48 hours to obtain a pale yellow transparent solid. This solid was subjected to Soxhlet extraction with methylene chloride. The volume shrinkage calculated from the density of the polymer before and after the reaction was 1.5%.

Reference Example 10 A glass vessel was charged with 572 mg of the polymer obtained in Example 6, 8.8 mg of di-t-butyl peroxide, and 2 mL of chlorobenzene, degassed, sealed, and heated at 120 ° C. for 48 hours to give a pale yellow transparent substance. A solid was obtained. This solid was subjected to Soxhlet extraction with methylene chloride. The volume shrinkage calculated from the density of the polymer before and after the reaction was 3.6%.

[0125]

According to the method of the present invention, there are provided a vinylcyclopropanone cyclic acetal compound and a poly (vinylcyclopropane acetal) which undergo radical ring-opening polymerization or crosslinking and exhibit a low volume shrinkage.

Continuation of front page (56) References Organic Chemical (1992), 57 (22), 5809-10. Am. Chemical Society (1990), 112 (20), 7428-30. Am. Chemical Society (1988), 110 (4), 1297-8 (58) Fields investigated (Int. Cl. ⁷ , DB name) CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] 1. A vinylcyclopropanone cyclic acetal compound represented by the following general formulas (1) to (14). Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) 2. Poly (vinylcyclopropane acetal) represented by the following general formulas (15) to (28). Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.) (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each represent a hydrogen atom or a lower alkyl group.)